JP7353981B2 - Blocking agents, latent hardeners and polyurethane compositions for amines - Google Patents

Description

The present invention relates to blocking agents for amines, latent hardeners and polyurethane compositions thereof, particularly for use as elastic adhesives, sealants and coatings.

Polyurethane compositions that are crosslinked through reaction of isocyanate groups with moisture or water and cured to give elastomers can be used, for example, for joining components in assemblies, for filling joints, as floor coatings or roofing. as adhesives, sealants or coatings in the construction and manufacturing industries. Due to their good adhesion and elasticity, they are able to gently dampen forces acting on the substrate caused by vibrations or temperature changes. However, when compositions of this type are used under high humidity and/or high temperatures, their curing often results in the formation of bubbles that cause rupture due to the release of carbon dioxide gas that does not dissolve or dissipate fast enough. It progresses with formation, which leads to loss of adhesion and strength. To avoid the formation of air bubbles, it is possible to add chemically blocked amines, called latent hardeners, to the composition. The amine binds water via hydrolysis, liberating amino groups that react with isocyanate groups without the formation of carbon dioxide. The latent curing agents used are usually compounds with aldimine, ketimine or oxazolidine groups. However, the known latent hardeners have the disadvantage that they are often highly viscous oils or solids at room temperature and therefore have high demands on their handling, e.g. they have to be melted or dissolved. has. Furthermore, they do not have sufficient latent potential and may therefore cause unexpectedly early crosslinking reactions of isocyanate groups in compositions containing isocyanate groups during storage, resulting in poor storage stability of the compositions. and/or the air drying time may be too short, accelerating curing to the point that the work frame becomes too small. Moreover, many of the known latent curing agents have a troublesome odor caused by highly volatile and odoriferous aldehydes or ketones that function as blocking agents in the latent curing agent and are released by hydrolysis during curing. brings about the introduction of

WO 2004/013200 discloses polyurethane compositions containing a latent curing agent, the blocking agent being non-volatile and thus remaining in the cured composition. These compositions are completely odorless and can therefore also be used for application to indoor spaces or large areas without problems with the introduction of odors. However, these have various drawbacks. Non-volatile blocking agents act as plasticizers in the cured composition, which can reduce mechanical strength or stiffness. When the content of plasticizer is high, plasticizer migration often increases, which is caused by smearing, stickiness, slightly stained surfaces of the composition, contamination or damage of the substrate or coating of the composition, This may be particularly evident in problems associated with overcoating, overcoating, recoating or overbonding.

Finally, non-volatile substances replacing volatile blocking agents also result in clearly higher costs. On the one hand, due to the high mass, quantitatively more blocking agent is required, and on the other hand, its purification is expensive, since expensive equipment is required, a long time is required, and This is because, for example, distillation must be carried out at high vacuum and high temperature, where yields are often low due to polymer formation and other decomposition reactions at high temperatures.

WO 2013/179915 describes branched long-chain alkylbenzaldehydes used as blocking agents in the amine component of epoxy resin compositions in distilled or fractionated form. In distillation or fractional distillation, as described in Example 2, the aldehyde is distilled overhead and collected as the main fraction with a boiling point of 187-230° C. at 8 Torr for further use. In this process, highly volatile fractions and especially high-boiling by-products were also separated.

Therefore, the present invention provides an inexpensive blocked amine that is liquid and low viscosity at room temperature, does not pose problems with odor introduction and plasticizer migration, and is storage stable even with isocyanate groups. The object of the present invention is to make available an economical blocking agent for amines, which also allows the preparation of latent curing agents.

This purpose is achieved by the blocking agent as claimed in claim 1, which is in the form of an aldehyde mixture containing an alkylbenzaldehyde as the main constituent and an additional predominantly high-boiling alkylbenzene compound as a minor constituent. achieved by. Aldehyde mixtures can be obtained, inter alia, as unpurified or only slightly purified crude products of the formylation of alkylbenzenes, which is very economical and allows high-boiling fractions to be It also results in a blocked amine that is significantly cheaper than if the corresponding stripped, purified blocking agent were used. Surprisingly, the properties of the blocked amines themselves and of the isocyanate group-containing compositions containing these blocked amines as latent curing agents are not impaired by the sub-constituents of the blocking agent according to the invention. Surprisingly, it has actually improved. Blocked amines according to the invention are typically liquid at room temperature and have a low viscosity, so they can be applied easily and without solvents. Surprisingly, they also have a lower viscosity than the latent curing agents prepared with the corresponding purified blocking agents after the high-boiling components have been removed, which results in higher molecular weight condensates. This is surprising in view of the resulting high molecular weight and partial aldehyde functionality of the secondary components. Furthermore, they have a low crystallization temperature, which allows them to remain liquid for very long periods of time when stored under cold conditions. Finally, they are surprisingly light in color and have a surprisingly good potential for isocyanates, despite the fact that there is no purification of the blocking agent.

The moisture-curing polyurethane composition formulated with the latent curing agent according to the present invention has a low viscosity, can be stored for a long period of time, can be easily processed, and has no odor problems even in indoor spaces. Can be used in large area and low emission applications and has long air drying time and fast curing. In the cured state they have good mechanical properties with high elasticity and a low tendency to plasticizer migration. Surprisingly, they exhibit even better mechanical properties such as viscosity, storage stability and above all strength when compared to similar compositions with latent hardeners derived from corresponding purified blocking agents. Show characteristics.

Further aspects of the invention are the subject of further independent claims. Particularly preferred embodiments of the invention are the subject of the dependent claims.

（式中、Ｒは、６～２０個の炭素原子を有するアルキル基である）
のアルデヒドと、
－ ５重量％～３０重量％の、式（Ｉ）に対応していないアルキルベンゼン化合物と
を含むアルデヒド混合物の、アミンのためのブロッキング剤としての使用を提供する。 The present invention
- 70% to 95% by weight of formula (I)

(wherein R is an alkyl group having 6 to 20 carbon atoms)
aldehyde and
- Provides for the use of aldehyde mixtures containing from 5% to 30% by weight of alkylbenzene compounds not corresponding to formula (I) as blocking agents for amines.

Preferably, the aldehyde mixture comprises 70% to 92% by weight of aldehydes of formula (I) and 8% to 30% by weight of alkylbenzene compounds not corresponding to formula (I).

In particular, alkylbenzene compounds that do not correspond to formula (I) have a higher boiling point than the aldehydes of formula (I).

Preferably R is an alkyl group having 8 to 16 carbon atoms, especially 10 to 14 carbon atoms.

Particularly preferably, R is an alkyl group having 10 to 14 carbon atoms, and the alkylbenzene compounds not corresponding to formula (I) have a molecular weight of at least 350 g/mol.

Preferably, the alkyl group R is predominantly branched.

In particular, R is a predominantly branched alkyl group having 10 to 14 carbon atoms. Such aldehydes inter alia result in blocked amines of low viscosity.

（式中、Ｒ^１及びＲ^２は、それぞれの場合にアルキル基であり、且つそれぞれの場合に一緒になって９～１３個の炭素原子を有する）
の基である。 Particularly preferably, R is of the formula

(wherein R ¹ and R ² are in each case an alkyl group and in each case together have from 9 to 13 carbon atoms)
It is the basis of

The formyl group is preferably in the meta or para position relative to the group R.

Particularly preferably the formyl group is in the para position.

（式中、Ｒ^１及びＲ^２は、既述の意味を有する）
のアルデヒドを表す。 Very preferably, the aldehyde of formula (I) is therefore of formula (Ia)

(In the formula, R ¹ and R ² have the meanings described above)
represents an aldehyde.

Particularly preferred aldehydes of formula (I) are 4-decylbenzaldehyde, 4-undecylbenzaldehyde, 4-dodecylbenzaldehyde, 4-tridecylbenzaldehyde and 4-tetradecylbenzaldehyde, where the 4-alkyl group is branched It is a type.

The aldehyde of formula (I) is preferably selected from 4-decylbenzaldehyde, 4-undecylbenzaldehyde, 4-dodecylbenzaldehyde, 4-tridecylbenzaldehyde and 4-tetradecylbenzaldehyde, the alkyl group of this aldehyde being predominantly It is a branched type.

Alkylbenzene compounds which do not correspond to formula (I) have a predominantly higher molecular weight than the aldehydes of formula (I) and are partially aldehyde functional.

（式中、Ｒ’は、６～２０個の炭素原子を有するアルキレン基であり、及びＲは、既述の意味を有する）
の１つ以上の化合物を含む。 Preferably these are the formula

(wherein R' is an alkylene group having 6 to 20 carbon atoms, and R has the meaning previously described)
containing one or more compounds.

Such high molecular weight compounds have substantially higher boiling points than the aldehydes corresponding to formula (I) (which are typically removed as a waste product called bottoms) and therefore require overhead distillation. or separated by purification of the mixture of aldehydes of formula (I) via fractional distillation. In the use according to the invention, however, aldehydes corresponding to formula (I) are used together with aldehydes of formula (I), which surprisingly results in the previously mentioned unexpected advantages. brought about.

（式中、Ｒ及びＲ’は、既述の意味を有する）
の化合物から選択されるアルキルベンゼン化合物を含む。 Particularly preferably, the aldehyde mixture contains from 5% to 30% by weight, especially from 8% to 30% by weight of the formula

(In the formula, R and R' have the meanings described above)
an alkylbenzene compound selected from the following compounds.

"Primary amino group" refers to an amino group that is attached to a single organic group and has two hydrogen atoms; "secondary amino group" refers to an amino group that is attached to a single organic group and has two hydrogen atoms; Also refers to an amino group bonded to a group and having one hydrogen atom; a "tertiary amino group" is bonded to three organic groups, two or three of which may also be part of one or more rings; Refers to an amino group that does not have any hydrogen atoms.

"Primary diamine" refers to a compound having two primary amino groups.

"Aromatic" refers to an amine or isocyanate in which the amino or isocyanate group is bonded directly to an aromatic carbon atom.

"Aliphatic" refers to an amine or isocyanate in which the amino or isocyanate group is bonded directly to an aliphatic carbon atom.

"Silane group" refers to a silyl group bonded to an organic group and having 1 to 3, especially 2 or 3 hydrolyzable alkoxy groups on the silicon atom.

"Molecular weight" refers to the molar mass (in g/mole) of a molecule or molecule residue. "Average molecular weight" refers to the number average molecular weight (M _n ) of a polydisperse mixture of oligomeric or polymeric molecules or molecular residues. It is typically measured using gel permeation chromatography (GPC) against polystyrene as a standard.

The dotted line in the formula in each case represents the bond between the substituent and the corresponding molecular group.

Material names beginning with "poly" such as polyamines, polyols, or polyisocyanates formally refer to materials containing two or more of the functional groups in the name per molecule.

A substance or composition is suitable for its use as a result of storage without any change in its use or use properties for an extended period of time, typically at least 3 months and up to 6 months. It is said to be "shelf-stable" or "storable" if it can be stored at room temperature in a suitable container for a period of 30 minutes or more.

"Room temperature" refers to a temperature of 23°C.

"Plasticizer" refers to a liquid or dissolved substance that is not chemically incorporated into the cured polymer and typically provides a plasticizing effect to the polymer.

（式中、Ｒは、既述の意味を有する）
の少なくとも１つのアルキルベンゼンのホルミル化の反応生成物である。 The aldehyde mixtures of use according to the invention are, inter alia, of the formula

(In the formula, R has the meaning described above)
is the reaction product of the formylation of at least one alkylbenzene.

In this connection, the reaction product is inter alia unpurified or, through a purification process such as extraction or inter alia distillation or fractional distillation, the main constituents (aldehydes of formula (I) as already mentioned) and minor components. The components (alkylbenzene compounds not corresponding to the formula (I) mentioned above, which represent by-products of the formylation) remain as much as possible in the reaction product and are purified only to the extent that they are not separated from each other. Ta. Such reaction products are also referred to below as "crude products".

Formylation is preferably carried out with carbon monoxide (CO) as the formylation reagent.

The formylation of alkylbenzenes is preferably carried out with carbon monoxide in the presence of hydrofluoric acid and boron trifluoride (HF-BF ₃ or HBF ₄ ) as acid catalysts. This process is particularly advantageous because it can be carried out under mild conditions and therefore proceeds particularly selectively. Because of the high vapor pressure, the catalyst can be easily separated and used again, thereby avoiding expensive purification and waste disposal as in other catalyst systems.

Preferably, the reaction is carried out at a carbon monoxide partial pressure of 5 to 50 bar, especially 10 to 30 bar and a temperature of -50 to +20°C, especially -30 to 0°C.

The molar ratio of alkylbenzene to HF to BF ₃ is preferably in the range 1 to (2.5 to 30) to (1 to 5), especially 1 to (3 to 25) to (1.1 to 3). .

The reaction product is preferably added to a mixture of ice and water and extracted using a solvent, especially an alkane such as hexane or heptane. The extract is then preferably freed of traces of acid by washing with water or an aqueous base and a solvent, such as an aqueous sodium hydroxide solution, and optionally any additional low molecular weight constituents present are then removed. , removed from the reaction mixture by distillation.

The crude product thus obtained is rendered colorless and transparent or light-coloured, optionally by suitable methods such as eg filtration or adsorption.

No additional purification of the crude product obtained in this way, in particular distillation or fractional distillation of the aldehyde of formula (I), is necessary, which is particularly advantageous with respect to production expenditure and costs.

The aldehyde mixture preferably comprises a content of an aldehyde of formula (I) ranging from 80% to 95% by weight and a content of an alkylbenzene not corresponding to formula (I) of from 5% to 20% by weight. Compounds.

The aldehyde mixture is preferably free of low molecular weight constituents and is therefore odorless. In particular, the aldehyde mixture is free of solvent, benzaldehyde and C _1-5 -alkylbenzaldehyde.

Preferably, the aldehyde mixture is light colored.

In particular, the aldehyde mixture has a Gardner standard color number according to DIN ISO 4630 of at most 12, preferably at most 10. The resulting latent hardeners are also suitable for light colored polyurethane compositions.

Preferably, the amines to be blocked for use according to the invention have at least one primary or secondary amino group.

Particularly preferably, the amine to be blocked contains at least one primary or secondary amino group and additionally at least one selected from primary amino groups, secondary amino groups, hydroxyl groups and silane groups. It has two reactive groups.

Such amines are particularly suitable as latent curing agents and/or crosslinking agents and/or adhesion promoters for compounds having reactive groups such as isocyanate groups. In blocked form, if moisture-proof, they do not react with such compounds or only react very slowly, on the other hand they can react hydrolytically on contact with moisture.

Amines suitable for blocking are inter alia primary aliphatic diamines, primary aromatic diamines, primary aliphatic triamines, aliphatic diamines with primary and secondary amino groups, two primary and aliphatic polyamines having secondary amino groups, amino alcohols, dialkanolamines, aminosilanes, and alkanol-aminosilanes.

Suitable primary aliphatic diamines are inter alia 1,2-ethanediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,3-butanediamine, 2-methyl -1,2-propanediamine, 1,3-pentanediamine, 1,5-pentanediamine, 2,2-dimethyl-1,3-propanediamine, 1,6-hexanediamine, 1,5-diamino-2- Methylpentane, 1,7-heptanediamine, 1,8-octanediamine, 2,5-dimethyl-1,6-hexanediamine, 1,9-nonanediamine, 2,2(4),4-trimethyl-1,6 -Hexanediamine, 1,10-decanediamine, 1,11-undecanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,12-dodecanediamine, 1,2-cyclohexanediamine, 1,3 -Cyclohexanediamine, 1,4-cyclohexanediamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 4(2)-methyl-1,3-cyclohexanediamine, 1,3-bis(amino methyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, bis(4-amino-3-ethylcyclohexyl)methane, Bis(4-amino-3,5-dimethylcyclohexyl)methane, bis(4-amino-3-ethyl-5-methylcyclohexyl)methane, 2,5(2,6)-bis(aminomethyl)bicyclo[2. 2.1] heptane, 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0 ^2,6 ]decane, 1,3-bis(aminomethyl)benzene, 1,4 -Bis(aminomethyl)benzene, 3-oxa-1,5-pentanediamine, 3,6-dioxaoctane-1,8-diamine, 4,7-dioxadecane-1,10-diamine, 4,7-dioxadecane -2,9-diamine, 4,9-dioxadodecane-1,12-diamine, 5,8-dioxadodecane-3,10-diamine, 4,7,10-trioxatridecane-1,13- diamines, α,ω-polyoxypropylene diamines having an average molecular weight in the range from 200 to 4000 g/mol (in particular Jeffamine® products D-230, D-400, XTJ-582, D-2000, XTJ-578 or D-4000 (all from Huntsman)), α,ω-polyoxypropylene/polyoxyethylenediamine (particularly the Jeffamine® products ED-600, ED-900, ED-2003 or HK-511 (all from Huntsman)) , α,ω-polyoxypropylene/polyoxy-1,4-butylene diamine (especially Jeffamine® products THF-100, THF-140, THF-230, XTJ-533 or XTJ-536 (all from Huntsman)) , α,ω-polyoxypropylene/polyoxy-1,2-butylene diamine (particularly the Jeffamine® products XTJ-568 or XTJ-569 (both from Huntsman)) or α,ω-polyoxy-1,2-butylene Diamines, especially Jeffamine® XTJ-523 (manufactured by Huntsman).

Suitable primary aromatic diamines are inter alia 1,3-phenylenediamine, 1,4-phenylenediamine, 4(2)-methyl-1,3-phenylenediamine (TDA), 3,5-diethyl-2 , 4(6)-toluenediamine (DETDA) or 4,4'-diaminodiphenylmethane (MDA).

Suitable primary aliphatic triamines are inter alia 1,3,6-triaminohexane, 1,4,8-triaminooctane, 4-aminomethyl-1,8-octanediamine, 5-aminomethyl-1 , 8-octanediamine, 1,6,11-triaminoundecane, 1,3,5-triaminocyclohexane, 1,3,5-tris(aminomethyl)cyclohexane, 1,3,5-tris(aminomethyl) Benzene, trimethylolpropane- or glycerol-starting tris(ω-polyoxypropylene amine) with an average molecular weight in the range from 380 to 6000 g/mol (especially Jeffamine® products T-403, T-3000 or T-5000) (all from Huntsman)) or trimethylolpropane-starting tris(ω-polyoxypropylene/polyoxy-1,2-butyleneamine) (especially Jeffamine® XTJ-566 (from Huntsman)).

Suitable aliphatic diamines with primary and secondary amino groups are, inter alia, N-methyl-1,2-ethanediamine, N-ethyl-1,2-ethanediamine, N-butyl-1,2-ethanediamine, Ethanediamine, N-hexyl-1,2-ethanediamine, N-(2-ethylhexyl)-1,2-ethanediamine, N-cyclohexyl-1,2-ethanediamine, N-benzyl-1,2-ethanediamine , 4-aminomethylpiperidine, 3-(4-aminobutyl)piperidine, N-(2-aminoethyl)piperazine, N-(2-aminopropyl)piperazine, N-benzyl-1,2-propanediamine, N- Benzyl-1,3-propanediamine, N-methyl-1,3-propanediamine, N-ethyl-1,3-propanediamine, N-butyl-1,3-propanediamine, N-hexyl-1,3- Propanediamine, N-(2-ethylhexyl)-1,3-propanediamine, N-dodecyl-1,3-propanediamine, N-cyclohexyl-1,3-propanediamine, 3-methylamino-1-pentylamine, 3-ethylamino-1-pentylamine, 3-butylamino-1-pentylamine, 3-hexylamino-1-pentylamine, 3-(2-ethylhexyl)amino-1-pentylamine, 3-dodecylamino-1 - pentylamine, 3-cyclohexylamino-1-pentylamine, fatty diamines, including N-cocoalkyl-1,3-propanediamine, N-oleyl-1,3-propanediamine, N-soyaalkyl-1,3 -propanediamine, N-tallow alkyl-1,3-propanediamine or N-(C _16-22 -alkyl)-1,3-propanediamine (for example available from Akzo Nobel under the trade name Duomeen®) or products of the Michael addition of aliphatic primary diamines to acrylonitrile, maleic or fumaric diesters, citraconic diesters, (meth)acrylic esters, (meth)acrylamides or itaconic diesters (molar ratio 1: 1), etc.).

Suitable aliphatic polyamines having two primary and secondary amino groups are inter alia bis(hexamethylene)triamine (BHMT), diethylenetriamine (DETA), dipropylenetriamine (DPTA), N-(2-amino ethyl)-1,3-propanediamine (N3-Amin), N3-(3-aminopentyl)-1,3-pentanediamine or N5-(3-amino-1-ethylpropyl)-2-methyl-1, 5-pentanediamine.

Suitable amino alcohols are inter alia 2-aminoethanol, 2-amino-1-propanol, 1-amino-2-propanol, 3-amino-1-propanol, 4-amino-1-butanol, 4-amino-2-propanol. -butanol, 2-amino-2-methylpropanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 7-amino-1-heptanol, 8-amino-1-octanol, 10-amino-1 -decanol, 12-amino-1-dodecanol or its higher homologs, 4-(2-aminoethyl)-2-hydroxyethylbenzene, 3-aminomethyl-3,5,5-trimethylcyclohexanol, primary glycols Derivatives having amino groups, such as diethylene glycol, dipropylene glycol, dibutylene glycol or higher oligomers or polymers of these glycols, especially 2-(2-aminoethoxy)ethanol, 2-(2-(2-aminoethoxy) ) ethoxy) ethanol or α-(2-hydroxymethylethyl)-ω-(2-aminomethylethoxy)poly(oxy(methyl-1,2-ethanediyl), 3-(2-hydroxyethoxy)propylamine, 3- (2-(2-hydroxyethoxy)ethoxy)propylamine or 3-(6-hydroxyhexyloxy)propylamine, N-methylethanolamine, N-ethylethanolamine, N-(n-propyl)ethanolamine, N- Isopropylethanolamine, N-(n-butyl)ethanolamine, N-isobutylethanolamine, N-(2-butyl)ethanolamine, N-(tert-butyl)ethanolamine, N-hexylethanolamine, N-isohexyl Ethanolamine or the reaction product of a monoepoxide with a primary aliphatic diamine such as N-(2-ethylhexyl)ethanolamine and N-(2-aminoethyl)ethanolamine or those mentioned above (1:1 molar ratio) , especially the reaction product of a superstoichiometric amount of 1,2-propanediamine or 2-methyl-1,5-pentanediamine with cresyl glycidyl ether, which is followed by unreacted 1,2-propane. diamines or 2-methyl-1,5-pentanediamine; furthermore, polyhydric amino alcohols, especially N,N'-dialkoxylation products of the above-mentioned primary aliphatic diamines, such as Jeffamine. (registered trademark) C-346 (manufactured by Huntsman), or N,N'-di-adducts of the above-mentioned primary aliphatic diamines with monoglycidyl ethers, in particular phenylglycidyl ether, cresylglycidyl ether, tert-butylphenyl glycidyl ether, cardanol glycidyl ether or 2-ethylhexyl glycidyl ether, or diglycidyl ethers (especially butanediol diglycidyl ether, hexanediol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, monoamines (such as bisphenol A diglycidyl ether or bisphenol F diglycidyl ether), especially isopropylamine, n-butylamine, isobutylamine, 2-butylamine, tert-butylamine, n-hexylamine, isohexylamine, 2-ethylhexylamine or It is an α,ω-diadduct with benzylamine, etc.).

Suitable dialkanolamines are, inter alia, diethanolamine, diisopropanolamine or 2-amino-2-ethyl-1,3-propanediol.

Suitable aminosilanes are, inter alia, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane or 3-aminopropyldimethoxymethylsilane.

Suitable alkanol aminosilanes are in particular alkoxylation products or adducts of the aminosilanes mentioned above with epoxides such as ethylene oxide, propylene oxide, phenyl glycidyl ether, cresyl glycidyl ether or alkyl glycidyl ether or especially 3-glycidoxypropyltritri Epoxysilanes such as methoxysilane or 3-glycidoxypropyltriethoxysilane.

Preferred amines for blocking are primary aliphatic diamines, primary aliphatic triamines or dialkanolamines.

Particularly preferred amines for blocking are diethanolamine, 1,6-hexanediamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 4(2)-methyl-1,3-cyclohexanediamine, 1, 3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)benzene, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexane Diamine, bis(4-aminocyclohexyl)methane, 2,5(2,6)-bis(aminomethyl)bicyclo[2.2.1]heptane, 3(4),8(9)-bis(aminomethyl) tricyclo[5.2.1.0 ^2,6 ]decane, α,ω-polyoxypropylene diamine with an average molecular weight ranging from 200 to 4000 g/mol (among others Jeffamine® products D-230, D-400) , XTJ-582, D-2000, XTJ-578 or D-4000 (all from Huntsman) and trimethylolpropane- or glycerol-started tris(ω-polyoxypropylene) with an average molecular weight in the range from 380 to 6000 g/mol. amines) (particularly the Jeffamine® products T-403, T-3000 or T-5000 (all from Huntsman)).

Among these, diethanolamine, 1,6-hexanediamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 1,3-bis(aminomethyl)benzene, with an average molecular weight of approximately 240 g/mol. Preference is given to α,ω-polyoxypropylene diamine with a trimethylolpropane-starting tris(ω-polyoxypropylene amine) with an average molecular weight of approximately 440 g/mol.

These amines are readily available in blocked form with low viscosity and exhibit good storage stability, good processability, fast curing with reasonable air drying time and high strength with surprisingly high extensibility among others. Achieving a polyurethane composition with excellent mechanical properties.

In the inventive use of an aldehyde mixture, the aldehyde mixture is preferably reacted with the amine to be blocked, thereby
- the aldehyde mixture is combined with the amine to give the reaction mixture, optionally with the addition of a solvent, the aldehyde groups being preferably stoichiometric or substoichiometric with respect to the primary or secondary amino groups; present in excess, and - the water of condensation produced in the reaction, and optionally the solvent used during or after the combination, is removed from the reaction mixture by optionally heating the reaction mixture and/or applying vacuum. removed using any suitable method.

Preferably, the water of condensation is removed from the heated reaction mixture without using a solvent by applying reduced pressure.

This reaction is preferably carried out at a temperature in the range from 20°C to 120°C, especially from 40°C to 100°C.

Optionally, a catalyst is used in the reaction, especially an acid catalyst.

A further object of the invention is blocked amines obtainable by the inventive use of the already mentioned aldehyde mixtures.

（式中、
Ｘは、Ｏ、又はＳ、又はＮＲ^０であり、ここで、Ｒ^０は、１～１８個の炭素原子を有する一価の有機基であり、
Ｙは、任意選択により置換されている１，２－エチレン又は１，３－プロピレン基であり、及び
Ｒは、既述の意味を有する）
の官能基を有する。 Blocked amines are inter alia those of formula (II) and/or (III)

(In the formula,
X is O, or S, or NR ⁰ , where R ⁰ is a monovalent organic group having 1 to 18 carbon atoms;
Y is an optionally substituted 1,2-ethylene or 1,3-propylene group, and R has the meaning given above)
It has a functional group of

Preferably, in the functional group of formula (II) or (III), R is in the meta or para position, especially in the para position.

Functional groups of formula (II) result from the condensation reaction of primary amino groups of aldehydes of formula (I). This represents an aldimino group.

The functional group of formula (III) results from the condensation reaction of the group ---NH--Y--XH with the aldehyde of formula (I), where Y and X have the meanings given above.

Preferably R ⁰ is an alkyl, cycloalkyl or arylalkyl group having 1 to 18 carbon atoms, which optionally includes carboxylic esters, nitriles, nitro, phosphonates, sulfones and sulfonic acids. It has one or two groups selected from ester groups.

Preferably, X is O.

Preferably NH and XH are separated from each other by two carbon atoms.

Such a functional group of formula (III) represents an oxazolidino group. It is particularly reactive when used as a latent curing agent in polyurethane compositions.

（式中、Ｅは、６～２０個の炭素原子を有する二価炭化水素基であり、これは、任意選択により、１つ以上のエーテル、エステル又はグリシドキシ基を有し、及びＲ^３は、１～３５個の炭素原子を有するアルキル、シクロアルキル又はアラルキル基であり、これは、任意選択により、１つ以上のエーテル基を有する）
の基でもあり得る。 Preferably, Y is a 1,2-ethylene, or 1,3-propylene, or 1,2-propylene group, or a 3-alkyloxy-1,2-propylene or 3-aryloxy-1,2 - a propylene group, the last two groups being optionally substituted and optionally carrying a silane group, or when n=1 and X=O, the formula

(wherein E is a divalent hydrocarbon group having 6 to 20 carbon atoms, which optionally carries one or more ether, ester or glycidoxy groups, and R ³ is an alkyl, cycloalkyl or aralkyl group having 1 to 35 carbon atoms, which optionally carries one or more ether groups)
It can also be the basis of

Particularly preferably, X is O and Y is a 1,2-ethylene or optionally substituted 3-alkyloxy-1,2-propylene or 3-aryloxy-1,2-propylene group It is.

Preferably R ³ is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 2-butyl, tert-butyl, n-hexyl, isohexyl, 2-ethylhexyl, dodecyl, benzyl or methoxy-terminated polyoxy A propylene group, which can also contain an oxyethylene fraction.

Preferably, E is 4,4'-methylenediphenyl, 4,4'-(2,2-propylene)diphenyl, 1,2-, or 1,3- with an average molecular weight in the range from 96 to 1000 g/mol. , or 1,4-phenyl, 1,4-butylene, 1,6-hexylene or α,ω-polyoxypropylene.

Blocked amines may be advantageously used as latent curing agents and/or crosslinking agents and/or adhesion promoters.

For use as an adhesion promoter, the blocked amine preferably contains at least one silane group. Adhesion promoters are particularly useful in employing compositions containing isocyanate and/or silane groups.

Preferably, blocked amines are used as latent curing agents for compositions containing reactive groups capable of reacting with amine hydrogens, such as isocyanate groups or epoxy groups, among others. For this use, blocked amines include, in addition to functional groups of formula (II) and/or (III), functional groups of formula (II) and/or (III), hydroxyl groups, mercapto groups, primary amino and at least one additional reactive group selected from the group consisting of secondary amino groups.

Preference is given to latent curing agents which have two or three functional groups of formula (II) and thereby represent dialdimines or trialdimines.

More preferred are latent curing agents which have a functional group of formula (II) and a hydroxyl group, or a primary amino group, or a secondary amino group, especially a hydroxyl group, thereby representing a hydroxyaldimine or an aminoaldimine.

Further preference is given to latent curing agents which have a functional group of formula (II) and a functional group of formula (III) and in particular represent an aldimino-oxazolidine.

More preferred are latent curing agents having two functional groups of formula (III) and especially representing bisoxazolidine.

More preferred are latent curing agents having a functional group of formula (III) and a hydroxyl group, especially representing hydroxyoxazolidine.

Particularly preferred are dialdimines, trialdimines, hydroxyaldimines, bisoxazolidines and hydroxyoxazolidines.

Most preferred are dialdimines and trialdimines, especially dialdimines.

Latent curing agents containing free OH or NH groups react when mixed with polyisocyanates to yield reaction products containing isocyanate groups, which as such represent latent curing agents and When moisture enters, it acts as a crosslinking agent.

のヒドロキシオキサゾリジンが得られる。 When diethanolamine is used as the amine to be blocked, the formula

of hydroxyoxazolidine is obtained.

（式中、Ｄは、６～１５個の炭素原子を有する二価炭化水素基、とりわけ１，６－ヘキサメチレン、又は（１，５，５－トリメチルシクロヘキサン－１－イル）メタン－１，３、又は４（２）－メチル－１，３－フェニレンであり、及びＲは、既述の意味を有する）
のビスオキサゾリジンをもたらすジイソシアネートとの反応又はカーボネートとの反応にとりわけ好適である。 Such hydroxyoxazolidines have the formula

(wherein D is a divalent hydrocarbon group having 6 to 15 carbon atoms, especially 1,6-hexamethylene or (1,5,5-trimethylcyclohexan-1-yl)methane-1,3 , or 4(2)-methyl-1,3-phenylene, and R has the meaning previously described)
It is particularly suitable for reaction with diisocyanates or with carbonates to give bisoxazolidines.

Latent curing agents are particularly suitable for compositions containing isocyanate groups, especially polyurethane compositions.

The latent curing agent contains, in addition to the functional groups of formula (II) and/or (III), additional functional groups derived from the condensation reaction of alkylbenzene compounds not corresponding to formula (I) with amino groups. Has a fraction. Surprisingly, these fractions do not have a negative effect on the use of latent curing agents, but on the contrary they provide advantages. Therefore, the latent curing agent has a lower viscosity and a lower crystallization temperature than the corresponding latent curing agent using purified blocking agent in the form of pure aldehyde of formula (I) for preparation. Therefore, a polyurethane composition with high strength and no adverse effect on storage stability was obtained.

An additional subject of the invention is a composition containing isocyanate groups comprising at least one blocked amine obtainable by the use described above.

（式中、
ｎは、２又は３であり、
Ａは、２８～１００００ｇ／モルの範囲の分子量を有するｎ価の有機基であり、及び
Ｒは、既述の意味を有する）
の少なくとも１つのポリアルジミンと
を含む。 Preferably, the composition containing isocyanate groups is
- at least one polyisocyanate and/or at least one polyurethane polymer containing isocyanate groups;
- Formula (IV),

(In the formula,
n is 2 or 3,
A is an n-valent organic group with a molecular weight in the range from 28 to 10,000 g/mol, and R has the meaning previously stated)
at least one polyaldimine.

Preferably R is in the meta or para position, especially in the para position.

Preferably, A is an n-valent hydrocarbon group with a molecular weight in the range from 28 to 6000 g/mol, optionally containing one or more groups selected from ether, ester, carbonate, urethane and urea groups. It has a group of

Preferably, n is 2.

Preferably, A is an n-valent aliphatic, cycloaliphatic or aryl fatty acid hydrocarbon group, optionally having an ether oxygen and having a molecular weight in the range from 28 to 6000 g/mol. Such aliphatic amine-based polyaldimines are particularly advantageous from a toxicological point of view.

Particularly preferably, A is 1,6-hexylene, (1,5,5-trimethylcyclohexan-1-yl)methane-1,3,4(2)-methyl-1,3-cyclohexylene, 1,3 -Cyclohexylenebis(methylene), 1,4-cyclohexylenebis(methylene), 1,3-phenylenebis(methylene), 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, Methylenebis(2-methylcyclohexan-4-yl), (bicyclo[2.2.1]heptane-2,5(2,6)-diyl)dimethylene, (tricyclo[5.2.1.0 ^2,6 ] Decane-3(4),8(9)-diyl)dimethylene, α,ω-polyoxypropylene with an average molecular weight ranging from 170 to 4000 g/mol and trimethylol with an average molecular weight ranging from 330 to 6000 g/mol Propane- or glycerol-starting tris(ω-polyoxypropylene).

A is inter alia 1,6-hexylene, (1,5,5-trimethylcyclohexan-1-yl)methane-1,3,1,3-cyclohexylenebis(methylene), 1,3-phenylenebis(methylene) ), α,ω-polyoxypropylene with an average molecular weight in the range from 170 to 470 g/mol and trimethylolpropane-starting tris(ω-polyoxypropylene) with an average molecular weight in the range from 330 to 450 g/mol selected from.

Such polyaldimines are, inter alia, readily available, have a low viscosity at room temperature and provide compositions with good mechanical properties, especially high strength and high extensibility.

Suitable polyisocyanates are, inter alia, commercially available polyisocyanates, in particular:
- aromatic di- or triisocyanates, preferably diphenylmethane 4,4'- or 2,4'- or 2,2'-diisocyanates or any mixtures of these isomers (MDI), toluylene 2,4- or 2, 6-diisocyanates or any mixtures of these isomers (TDI), mixtures of MDI and MDI homologs (polymeric MDI or PMDI), phenylene 1,3- or 1,4-diisocyanates, 2,3,5,6 -tetramethyl-1,4-diisocyanatobenzene, naphthalene 1,5-diisocyanate (NDI), 3,3'-dimethyl-4,4'-diisocyanatodiphenyl (TODI), dianisidine diisocyanate (DADI), Tris(4-isocyanatophenyl)methane or tris(4-isocyanatophenyl)thiophosphate; preferably MDI or TDI;
- aliphatic, cycloaliphatic or arylaliphatic di- or triisocyanates, preferably tetramethylene 1,4-diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, hexamethylene 1,6-diisocyanate (HDI), 2, 2,4- and/or 2,4,4-trimethylhexamethylene 1,6-diisocyanate (TMDI), decamethylene 1,10-diisocyanate, dodecamethylene 1,12-diisocyanate, lysine diisocyanate or lysine ester diisocyanate, cyclohexane 1, 3- or 1,4-diisocyanate, 1-methyl-2,4- and/or 2,6-diisocyanatocyclohexane (H ₆ TDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanato Methylcyclohexane (IPDI), perhydrodiphenylmethane 2,4'- and/or 4,4'-diisocyanate (H ₁₂ MDI), 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane, m- or p -xylylene diisocyanate, tetramethylxylylene 1,3- or 1,4-diisocyanate, 1,3,5-tris(isocyanatomethyl)benzene, bis(1-isocyanato-1-methylethyl)naphthalene, especially 3, Dimeric or trimer fatty acid isocyanates such as 6-bis(9-isocyanatononyl)-4,5-di(1-heptenyl)cyclohexene (dimeryl diisocyanate); preferably H ₁₂ MDI or HDI or IPDI;
- oligomers or derivatives of the di- or triisocyanates mentioned, especially derived from HDI, IPDI, MDI or TDI, especially containing uretdione or isocyanurate or iminooxadiazinedione groups or various groups therein; oligomers; or esters, or ureas, or urethanes, or biurets, or allophanates, or carbodiimides, or uretonimines, or oxadiazinetrione groups or difunctional or polyfunctional derivatives containing various groups therein. In practice, polyisocyanates of this type are typically mixtures of materials with different degrees of oligomerization and/or chemical structure. They especially have an average NCO functionality of 2.1 to 4.0.

As polyisocyanates, preference is given to aliphatic, cycloaliphatic or aromatic diisocyanates, especially HDI, IPDI, H ₁₂ MDI, TDI or MDI, especially HDI, IPDI, TDI or MDI.

Suitable polyurethane polymers containing isocyanate groups are obtained, inter alia, from the reaction of at least one polyol with a superstoichiometric amount of at least one polyisocyanate. This reaction is preferably carried out at a temperature in the range from 50 to 160° C. with exclusion of moisture, optionally in the presence of a suitable catalyst. The NCO/OH ratio preferably ranges from 1.3/1 to 2.5/1. The polyisocyanates remaining in the reaction mixture after conversion of the OH groups, especially the monomeric diisocyanates, can be removed by distillation, which is preferred in the case of high NCO/OH ratios. The polyurethane polymer obtained preferably has a content of free isocyanate groups ranging from 0.5% to 10% by weight, especially from 1% to 5% by weight, particularly preferably from 1% to 3% by weight. . Polyurethane polymers can optionally be prepared with the additional use of plasticizers or solvents, in which case the plasticizers or solvents used do not contain any groups that are highly reactive towards isocyanates.

As polyisocyanates for the preparation of polyurethane polymers containing isocyanate groups, preference is given to the polyisocyanates already mentioned, especially the diisocyanates, preferably MDI, TDI, IPDI or HDI.

Suitable polyols are commercially available polyols or mixtures thereof, especially:
- polyether polyols, especially polyoxyalkylene diols and/or polyoxyalkylene triols, especially ethylene oxide, or 1,2-propylene oxide, or 1,2- or 2,3-butylene oxide, or oxetane, or tetrahydrofuran, or Polymerization product of a mixture of. Here, these are starter molecules with two or more active hydrogen atoms, in particular water, ammonia or compounds with a large number of OH or NH groups, such as 1,2-ethanediol, 1,2- or 1,3- Propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, isomer dipropylene glycol or tripropylene glycol, isomer butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanediol, 1 , 3- or 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerol or aniline or mixtures of the aforementioned compounds. can be polymerized using a starter molecule of Likewise suitable are polyether polyols with polymer particles dispersed therein, especially styrene/acrylonitrile (SAN) particles, or polyurea or polyhydrazodicarbonamide (PHD) particles dispersed therein.

Preferred polyether polyols are those referred to as polyoxypropylene diols or triols or ethylene oxide terminated (EO-endcapped) polyoxypropylene diols or triols. The latter is obtained inter alia by further alkoxylation of polyoxypropylene diols or triols with ethylene oxide at the end of the polypropoxylation reaction, thereby finally producing mixed polyoxyethylene/polyoxyethylene with primary hydroxyl groups. It is oxypropylene polyol.

Preferred polyether polyols have a degree of unsaturation of less than 0.02 meq/g, especially less than 0.01 meq/g.

- Polyester polyols, also called oligoesterols, prepared by known methods, in particular by polycondensation of hydroxycarboxylic acids or lactones or of aliphatic and/or aromatic polycarboxylic acids with dihydric or polyhydric alcohols. Especially 1,2-ethanediol, diethylene glycol, 1,2-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, glycerol, 1, dihydric alcohols such as 1,1-trimethylolpropane or mixtures of the aforementioned alcohols and in particular succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid , terephthalic acid or hexahydrophthalic acid or mixtures of the aforementioned acids or in particular polyester polyols from lactones such as ε-caprolactone. Particular preference is given to polyester polyols of adipic acid or sebacic acid or dodecanedicarboxylic acid and hexanediol or neopentyl glycol.

- used for example - to form polyester polyols - polycarbonate polyols such as those obtained by reaction of the alcohols mentioned above with dialkyl carbonates, diaryl carbonates or phosgene.

- Block copolymers with at least two different blocks, especially polyether polyester polyols, having at least two hydroxyl groups and having a polyether, polyester and/or polycarbonate structure of the type mentioned above.

- Polyacrylate polyols and polymethacrylate polyols.

- polyhydroxy-functional fats and oils, such as natural fats and oils, especially castor oil; or polyols obtained by chemical modification of natural fats and oils - called oleochemical polyols, - for example epoxidation of unsaturated oils and subsequent carvone Epoxy polyesters or epoxy polyethers obtained by ring opening with acids or alcohols or polyols obtained by hydroformylation and hydrogenation of unsaturated oils; or decomposition processes such as alcoholysis or ozonolysis and their thus obtained. Polyols obtained from natural fats and oils by subsequent chemical combination of decomposition products or derivatives, for example by transesterification or dimerization. Suitable breakdown products of natural fats and oils are, inter alia, fatty acids and fatty alcohols and also fatty acid esters, especially methyl esters (FAME), which are derivatized to hydroxy fatty acid esters, for example by hydroformylation and hydrogenation. be able to.

- polyhydrocarbon polyols, also called oligohydrocarbonols, such as polyhydroxy-functional polyolefins, polyisobutylene, polyisoprene; polyhydroxy-functional ethylene/propylene, ethylene/butylene or ethylene/ Propylene/diene copolymers; polyhydroxy-functional polymers of dienes, especially 1,3-butadiene, which can also be prepared inter alia from anionic polymerization; dienes or diene mixtures such as 1,3-butadiene with styrene, acrylonitrile, vinyl chloride , polyhydroxy-functional acrylonitrile/as can be prepared, for example, from polyhydroxy-functional copolymers with vinyl monomers such as vinyl acetate, vinyl alcohol, isobutylene and isoprene, such as epoxides or amino alcohols, and carboxyl-terminated acrylonitrile/butadiene copolymers. Butadiene copolymers (commercially available from Emerald Performance Materials under the name Hypro® CTBN or CTBNX or ETBN); and hydrogenated polyhydroxy functional polymers or copolymers of dienes.

Mixtures of polyols are also particularly suitable.

Preferred are polyether polyols, polyester polyols, polycarbonate polyols, poly(meth)acrylate polyols or polybutadiene polyols.

Particular preference is given to polyether polyols, polyester polyols, especially aliphatic polyester polyols or polycarbonate polyols, especially aliphatic polycarbonate polyols.

Most preferred are polyether polyols, especially polyoxypropylene di- or triols or ethylene oxide-terminated polyoxypropylene di- or triols.

Polyols having an average molecular weight in the range from 400 to 20,000 g/mol, preferably from 1,000 to 15,000 g/mol are preferred.

Polyols with an average OH functionality in the range 1.6 to 3 are preferred.

Polyols that are liquid at room temperature are preferred.

In the preparation of polyurethane polymers containing isocyanate groups, difunctional or polyfunctional alcohols, especially 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3- Propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,3-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, Neo Pentyl glycol, dibromoneopentyl glycol, 1,2-hexanediol, 1,6-hexanediol, 1,7-heptanediol, 1,2-octanediol, 1,8-octanediol, 2-ethyl-1,3 - hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, 1,3- or 1,4-cyclohexanedimethanol, ethoxylated bisphenol A, propoxylated bisphenol A, cyclohexanediol, hydrogenated bisphenol A, Dimeric fatty acid alcohols, sugar alcohols such as 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerol, pentaerythritol, especially xylitol, sorbitol or mannitol, or especially sugars such as sucrose, or It is also possible to use alkoxylated derivatives of the alcohols mentioned or fractions of mixtures of the alcohols mentioned.

The polyurethane polymers containing isocyanate groups preferably have an average molecular weight of 1500 to 20 000 g/mol, especially 2000 to 15 000 g/mol.

It is preferably liquid at room temperature.

For use in hot melt adhesives, polyurethane polymers that are solid at room temperature are preferred, which polymers are prepared starting from at least one polyol that is solid at room temperature. Suitable polymers that are solid at room temperature are crystalline, partially crystalline or amorphous at room temperature. Its melting point is preferably in the range of 50 to 180°C, especially 70 to 150°C. Polyester polyols are preferred, especially those derived from hexanediol and adipic acid, or dodecanedioic acid, or acrylate polyols. Polyurethane polymers are especially prepared at temperatures above the melting point of polymers that are solid at room temperature.

Preferably, the composition comprises at least one polyurethane polymer containing isocyanate groups.

In addition to the polyurethane polymer containing isocyanate groups, the composition comprises at least one diisocyanate and/or one oligomer or polymer of a diisocyanate, in particular an IPDI isocyanurate or a TDI oligomer or a mixed isocyanurate based on TDI/HDI or an HDI oligomer or It is possible to further include a form of MDI that is liquid at room temperature.

One form of MDI that is liquid at room temperature is 4,4'-MDI or 4,4'-MDI and other Mixtures with MDI isomers (2,4'-MDI and/or 2,2'-MDI) and/or MDI oligomers and/or MDI homologues (selectively brought about by blending or resulting from manufacturing processes) PMDI).

Preferably, the composition comprises, in addition to at least one polyisocyanate and/or polyurethane polymer containing isocyanate groups and at least one polyaldimine of formula (IV), additionally inter alia catalysts, fillers, plasticizers and solvents. and one or more additional selected components.

Suitable catalysts are in particular catalysts for the hydrolysis of aldimino groups, especially organic acids, especially 2-ethylhexanoic acid, lauric acid, stearic acid, isostearic acid, oleic acid, neodecanoic acid, benzoic acid, salicylic acid or 2-nitro Carboxylic acids such as benzoic acid, organic carboxylic anhydrides such as phthalic anhydride, hexahydrophthalic anhydride or methylhexahydrophthalic anhydride, silyl esters of carboxylic acids, methanesulfonic acid, p-toluenesulfonic acid or - organic sulfonic acids such as dodecylbenzenesulfonic acid, sulfonic acid esters, other organic or inorganic acids or mixtures of the aforementioned acids and acid esters. Particular preference is given to carboxylic acids, especially aromatic carboxylic acids such as benzoic acid, 2-nitrobenzoic acid or especially salicylic acid.

Suitable catalysts are furthermore catalysts for accelerating the reaction of isocyanate groups, in particular dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dibutyltin diacetylacetonate, dimethyltin dilaurate, dioctyltin diacetate, dioctyltin dilaurate or dioctyltin. Organotin(IV) compounds such as diacetylacetonates, especially with ligands selected from alkoxides, carboxylates, 1,3-diketonates, oxynates, 1,3-ketoesterates and 1,3-ketoamidates. , bismuth(III) or zirconium(IV) complexes or especially compounds containing tertiary amino groups such as 2,2'-dimorpholinodiethyl ether (DMDEE).

Combinations of different catalysts are also particularly suitable.

Suitable fillers are inter alia finely divided or precipitated calcium carbonate or barite, quartz powder, quartz sand, dolomite, wollastonite, kaolin, calcined kaolin, mica, optionally coated with fatty acids, especially stearates. or layered silicates such as talc, zeolites, aluminum hydroxide, magnesium hydroxide, silica such as finely divided silica from pyrogenic processes, cement, gypsum, fly ash, industrially produced carbon black, graphite, e.g. aluminum, copper. , iron, silver or steel metal powder, PVC powder or hollow beads.

Suitable plasticizers are, inter alia, phthalates, especially diisononyl phthalate (DINP), diisodecyl phthalate (DIDP) or di(2-propylheptyl) phthalate (DPHP), hydrogenated phthalates, especially hydrogenated diisononyl phthalate or diisononylcyclohexane-1, Carboxylic acid esters such as 2-dicarboxylic acid esters (DINCH), terephthalates, especially dioctyl terephthalate, trimellitate, adipate, especially dioctyl adipate, azelate, sebacate, benzoate, glycol ethers, glycol esters, organic phosphoric acid or sulfonic acid esters, polybutenes, Plasticizers derived from polyisobutene or natural fats or oils, especially epoxidized soybean oil or linseed oil.

Suitable solvents are inter alia acetone, methyl ethyl ketone, methyl n-propyl ketone, diisobutyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, methyl isoamyl ketone, acetylacetone, mesityl oxide, cyclohexanone, methylcyclohexanone, ethyl acetate, propyl acetate, butyl Acetate, n-butyl propionate, diethyl malonate, 1-methoxy-2-propyl acetate, ethyl 3-ethoxypropionate, diisopropyl ether, diethyl ether, dibutyl ether, diethylene glycol diethyl ether, ethylene glycol diethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono(2-ethylhexyl) ether, toluene, xylene, heptane, octane, naphtha, white spirit, petroleum ether or petroleum spirit, especially the Solvesso ^TM products (from Exxon) and also methylene chloride, propylene carbonate, Butyrolactone, N-methylpyrrolidone or N-ethylpyrrolidone.

The composition may contain further additives commonly used for polyurethane compositions. More specifically, the following auxiliaries and additives may be present:
- inorganic or organic pigments, especially titanium dioxide, chromium oxide or iron oxide;
- fibers, especially polymeric fibers such as glass fibers, carbon fibers, metal fibers, ceramic fibers, polyamide fibers or polyethylene fibers or natural fibers such as wool, cellulose, hemp or sisal;
- dye;
- desiccants, especially highly reactive isocyanates or orthoformates, such as molecular sieve powder, calcium oxide, p-tosyl isocyanate, monomeric diisocyanates;
- adhesion promoters, in particular organoalkoxysilanes, especially epoxysilanes such as 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropyltriethoxysilane, (meth)acrylosilanes, anhydridosilanes, carbamatosilanes, alkylsilanes or iminosilanes or oligomeric forms or titanates of these silanes;
- further latent curing agents or crosslinking agents, especially aldimines, ketimines, enamines or oxazolidines;
- further catalysts accelerating the reaction of isocyanate groups, in particular salts, soaps or complexes of tin, zinc, bismuth, iron, aluminium, molybdenum, dioxomolybdenum, titanium, zirconium or potassium, in particular tin(II) 2-ethylhexano ate, tin(II) neodecanoate, zinc(II) acetate, zinc(II) 2-ethylhexanoate, zinc(II) laurate, zinc(II) acetylacetonate, aluminum lactate, aluminum oleate, diisopropoxytitanium bis (ethylacetoacetate) or potassium acetate; compounds containing tertiary amino groups, especially N-ethyldiisopropylamine, N,N,N',N'-tetramethylalkylenediamine, pentamethylalkylenetriamine and higher homologs thereof , bis(N,N-diethylaminoethyl)adipate, tris(3-dimethylaminopropyl)amine, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0 ] Undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), N-alkylmorpholine, N,N'-dimethylpiperazine; 4-dimethylaminopyridine, Aromatic nitrogen compounds such as N-methylimidazole, N-vinylimidazole or 1,2-dimethylimidazole; Organic ammonium compounds such as benzyltrimethylammonium hydroxide or alkoxylated tertiary amines; Modification of known metal or amine catalysts , called “delayed action” catalysts;
- rheology modifiers, especially thickeners, especially layered silicates such as bentonites, derivatives of castor oil, hydrogenated castor oil, polyamides, polyamide waxes, polyurethanes, urea compounds, fumed silica, cellulose ethers or hydrophobically modified polyoxyethylene;
- fats or oils such as natural resins, rosin, shellac, linseed oil, castor oil or soybean oil;
- homopolymers or copolymers of unsaturated monomers, especially of non-reactive polymers, especially ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate or alkyl (meth)acrylates, especially polyethylene (PE), polypropylene (PP), poly Isobutylene, ethylene/vinyl acetate copolymer (EVA) or atactic poly-α-olefin (APAO);
- flame-retardant substances, in particular the already mentioned aluminum hydroxide or magnesium hydroxide, and also in particular organophosphate esters, such as in particular triethyl phosphate, tricresyl phosphate, triphenyl phosphate, diphenyl cresyl phosphate, isodecyl diphenyl phosphate, Tris (1,3-dichloro-2-propyl) phosphate, tris (2-chloroethyl) phosphate, tris (2-ethylhexyl) phosphate, tris (chloroisopropyl) phosphate, tris (chloropropyl) phosphate, isopropylated triphenyl phosphate, organophosphate esters or ammonium polyphosphates such as mono-, bis- or tris(isopropylphenyl) phosphate, resorcinol bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate) with different degrees of isopropylation;
- additives, in particular wetting agents, leveling agents, antifoaming agents, deaerators, stabilizers against oxidative, thermal, light or UV radiation or biocides;
or further substances customarily used in moisture-curing compositions.

It may be reasonable to dry certain substances chemically or physically before incorporating them into the composition.

Polyaldimines derived from 2,2-dimethyl-3-lauroyloxypropanal are particularly suitable as further latent hardeners.

In the composition, the ratio of aldimino groups to isocyanate groups is preferably in the range from 0.05 to 1.1, particularly preferably from 0.1 to 1.0, especially from 0.2 to 0.9.

The composition preferably contains a content of polyisocyanate and a polyurethane polymer containing isocyanate groups ranging from 5% to 90% by weight, especially from 10% to 80% by weight.

The composition is, inter alia, manufactured to the exclusion of moisture and stored at ambient temperature in a waterproof container. Suitable waterproof containers are, inter alia, made of metal and/or plastic, optionally coated, and are inter alia drums, shipping boxes, hobbocks, buckets, canisters, cans, bags, tubular bags, cartridges or tubes.

The composition may be in the form of a one-component composition or a multi-component, especially two-component composition.

Compositions referred to as "one-component" compositions are those in which all components of the composition are in the same container and are storage stable as such.

Compositions referred to as "two-component" compositions are those in which the components of the composition are in two separate components, stored in separate containers, and not mixed together until immediately before or during application of the composition. .

The composition is preferably a one-component composition. Assuming suitable packaging and storage, it is typically shelf-stable for several months, up to a year or more.

Once the composition is applied, the curing process begins. This results in a cured composition.

In the case of a one-component composition, it is applied as such and then begins to harden under the influence of moisture or water. To accelerate curing, water-containing or releasing accelerator components and/or catalysts can be incorporated into the composition at the time of application, or the composition can be contacted with such accelerator components after its application. can be done.

In the case of a two-component composition, it is applied after mixing the two components and begins to cure by internal reaction, and curing can be completed by the action of external moisture. The two components can be mixed continuously or batchwise using dynamic or static mixers.

In curing, the isocyanate groups react, under the influence of moisture, with the aldimine groups of the polyaldimine of formula (IV) and any further blocked amino groups present. Some of the isocyanate groups in excess relative to the isocyanate groups, especially the aldimino groups, react with each other and/or with any further reactive groups present in the composition, especially hydroxyl groups or free amino groups, under the influence of moisture. The totality of these reactions of isocyanate groups leading to hardening of the composition is also called crosslinking.

The moisture required for curing the one-component composition preferably reaches the composition via diffusion from the air (atmospheric humidity). In this process, a solid layer of cured composition is formed on the surface of the composition that is in contact with the air (the "skin"). Curing proceeds in a diffusion direction from the outside to the inside, with the skin becoming progressively thicker and eventually encompassing the entire applied composition. Moisture may also reach the composition additionally or entirely from one or more substrates to which the composition is applied, and/or the moisture may be mixed into the composition at the time of application; Or it can originate from an accelerator component that is contacted after application, for example by painting or spraying.

Preferably, any external moisture required to complete curing of the two-component composition comes from air and/or the substrate.

The composition is preferably applied at ambient temperature, especially in the range of about 0-50°C, preferably in the range of 5-40°C.

If the composition is a hot melt adhesive, it is preferably applied in the molten state at a temperature in the range from 80 to 180°C.

The composition is preferably cured at ambient temperature.

The composition has a relatively long open time.

"Open time" refers to the period during which the composition can be processed or reprocessed after the curing process has begun.

The time until a skin forms ("skin time") or until tack is no longer present ("tack-free time") is a measure of open time.

Upon crosslinking, the blocking agent described, ie the aldehyde mixture, is released. It is substantially non-volatile, odorless, and remains largely in the cured composition. It behaves or behaves like a plasticizer. Therefore, it can in principle migrate itself and/or influence the migration of the plasticizer. The blocking agent has a very good affinity for the cured composition and hardly migrates itself and does not cause any increase in the migration of further plasticizers.

The composition is preferably an adhesive or sealant or coating.

The adhesive or sealant or coating is preferably elastic.

The compositions are particularly useful in the construction and manufacturing industry or in motor vehicle construction, especially for parquet joints, implementable component joints, cavity sealing, assemblies, module joints, vehicle body joints, window pane joints or joint sealing. It is particularly suitable as an adhesive and/or sealant for bonding and sealing applications.

Elastic connections in power vehicle construction are used, for example, for the attachment of parts such as plastic covers, decorative strips, flanges, mudguards, cabs or other implementable components by bonding to the painted body of the power vehicle or the car body. The joining of glass panes to a motor vehicle, where the motor vehicle is, inter alia, a car, truck, bus, rail car or ship.

The composition is particularly suitable as a sealant for the elastic sealing of all types of joints, seams or cavities relating to joints in architecture, such as inter alia expansion joints or interlocking joints between structural components. Sealants with flexible properties are particularly suitable for sealing expansion joints in built structures, among others.

As a coating, the composition can be applied to roofs, inter alia as a coating for balconies, terraces, open spaces, bridges, parking surfaces, for the protection of floors or walls, or inter alia as flat or slightly sloping roof areas or roof gardens. or for waterproof sealing inside buildings (e.g. under tiles or paving stones in plumbing units or kitchens) or as floor coverings in kitchens, industrial buildings or manufacturing spaces, or as collection tanks, Suitable as a seal in channels, shafts or wastewater treatment plants or for the protection of surfaces, for example as varnishes or seals or as a casting compound for cavity sealing, as a seam seal or as a protective coating for pipes.

The compositions may also be used for repair purposes, for example as seals or coatings on leaking roof sheets or floor coverings that are no longer fit for purpose, or for highly reactive spray seals, among others. Can be used as a repair compound.

The composition can be formulated so that it has a pasty consistency due to structural viscous properties. Compositions of this type are applied using suitable devices, eg in the form of beads, which may have a substantially round or triangular cross-section, eg from commercially available cartridges or kegs or hobbocks.

The composition can be further formulated so that it is fluid and "self-leveling" or only slightly thixotropic, and can be poured out for application. As a coating, it can, for example, then be spread flat, for example using a roller, slider, comb applicator or trowel, until the desired layer thickness is reached. In one operation, layer thicknesses typically range from 0.5 to 3 mm, especially from 1.0 to 2.5 mm.

Suitable substrates that can be bonded or sealed or coated with the composition include, among others:
- glass, glass-ceramic, concrete, mortar, fiber cement, especially fiber cement boards, bricks, tiles, plaster, especially gypsum boards or natural stones such as granite or marble;
- repair or leveling compounds based on PCC (polymer modified cement mortar) or ECC (epoxy resin modified cement mortar);
- metals or alloys such as aluminium, copper, iron, steel, non-ferrous metals or alloys such as galvanized or chromed metals, including surface finishing metals;
- asphalt or bitumen;
- further materials called leather, textiles, paper, wood, wood-based materials bonded with resins such as phenolic resins, melamine resins or epoxy resins, resin/textile composites or polymer composites;
- hard and flexible PVC, polycarbonate, polystyrene, polyester, polyamide, PMMA, ABS, SAN, epoxy resins, phenolic resins, PUR, POM, TPO, in each case untreated or surface-treated, for example by plasma, corona or flame; , PE, PP, EPM or EPDM;
- Fiber reinforced plastics such as carbon fiber reinforced plastics (CFP), glass fiber reinforced plastics (GFP) and sheet molding compounds (SMC);
- insulating foams made inter alia of EPS, XPS, PUR, PIR, rock wool, glass wool or foam glass;
- coated or painted substrates, in particular painted tiles, coated concrete, powder-coated metals or alloys or painted metal sheets;
- Paints or varnishes, especially automotive top coats.

If desired, the substrate can be pretreated before application by, inter alia, physical and/or chemical cleaning methods or the application of activators or primers.

It is possible to join and/or seal two identical or two different substrates.

Application and curing of the composition provides an article bonded or sealed or coated with the composition. The article may be a built structure or a part thereof, in particular above or below ground, in civil engineering, bridges, roofs, stairs or facades, or it may be an industrial or consumer good, in particular windows, pipes, wind turbines. It may be a rotary wing blade of a household appliance or a means of transport such as, in particular, a car, bus, truck, rail vehicle, ship, aircraft or helicopter, or an implementable component thereof.

The composition according to the invention has advantageous properties. The composition is moisture-tight and storage stable even with highly reactive aromatic isocyanate groups. The composition has a sufficiently long air drying time to allow the material to be spread seamlessly or to allow for positioning or readjustment of objects joined together over a period of time after application; This is important, for example, when coating large areas or long sealing strips or when joining large or complex objects. Curing proceeds quickly, reliably, and without the introduction of noxious odors and without the formation of bubbles, thus making the composition suitable for climatic conditions such as high air humidity and/or high temperatures. It can be used without any particular restrictions even under conditions where there is no water-based accelerator component or when an aqueous accelerator component is used, and it can be used without hesitation even when applied to indoor spaces or large areas. It is possible. Upon curing, the composition rapidly gains strength and the skin that forms on the surface becomes surprisingly non-tacky and dry very quickly, which prevents contamination by e.g. It is of great value, especially for applications on construction sites, as it prevents Curing proceeds to completion, resulting in a high quality material that combines high mechanical strength and extensibility with a moderate modulus of elasticity, and is therefore also suitable for flexible products. Despite containing liberated non-volatile blocking agents, the compositions exhibit very little of any of the defects caused by plasticizer migration such as smearing, discoloration, stain formation, softening or substrate detachment. Therefore, even porous substrates or plastics that form stress cracks and in combination with an outer layer can be used without particular limitation.

Exemplary embodiments are described below and are intended to further illustrate the invention as described. Naturally, the invention is not limited to these exemplary embodiments described.

"Standard climatic conditions" refer to a temperature of 23±1° C. and a relative air humidity of 50±5%.

Description of measurement method:
Amine values (including blocked amino groups) were determined by titration (0.1 N HClO ₄ in acetic acid versus crystal violet).

Viscosity was measured with a constant temperature Rheotec RC30 cone-plate viscometer (cone diameter 50 mm, cone angle 1°, cone tip plate distance 0.05 mm, shear rate 10 s ^-1 ).

The crystallization temperature or glass transition temperature was measured by DSC using a Mettler Toledo DSC 3+700 device in a temperature range of -80 to +50° C. and a heating rate of 5 K/min.

Aldehyde used:
Aldehyde-1: Crude product from HF- _BF catalyzed formylation of C _10-14 -alkylbenzenes with carbon monoxide after distillative separation of low molecular weight constituents, 85%-90% by weight mainly branched Contains 4-(C _10-14 -alkyl)benzaldehyde and 10% to 15% by weight of high boiling point or high molecular weight alkylbenzene compounds (measured by GC-FID); Average aldehyde equivalent weight 309 g/equivalent; Gardner standard color number 10 .
Aldehyde-2: Fractionated aldehyde mixture derived from overhead distillation of aldehyde-1 under high vacuum, containing >98% by weight of predominantly branched 4-(C _10-14 -alkyl)benzaldehydes (measured by GC-FID) ; Average aldehyde equivalent weight: 290 g/equivalent; Gardner standard color number: 3.
Aldehyde-3: 2,2-dimethyl-3-lauroyloxypropanal (284.4 g/mol)

Aldehyde-1 is an aldehyde mixture according to the invention. The corresponding distillation-purified aldehydes-2 and aldehydes-3 from which the high-boiling by-products were separated are also used as comparisons.

Preparation of blocked amines or latent curing agents:
Aldimine A-1:
106.06 g of aldehyde-1 was introduced into the round bottom flask under nitrogen atmosphere. 27.86 g of 3-aminomethyl-3,5,5-trimethylcyclohexylamine (Vestamin® IPD, from Evonik) are added with stirring, after which the volatile components are removed at 80° C. and under reduced pressure of 10 mbar. It was removed with . A light-colored, odorless liquid was obtained with a viscosity of 10.7 Pa·s at 20°C, an amine value of 143.5 mg KOH/g and a crystallization temperature of -46.1°C.

Aldimine A-2:
106.06 g of aldehyde-1 was introduced into the round bottom flask under nitrogen atmosphere. 27.20 g of a 70% aqueous solution of 1,6-hexanediamine (from Sigma-Aldrich) were added with stirring, after which the volatile constituents were removed at 80° C. and under reduced pressure of 10 mbar. A light-colored, odorless liquid was obtained with a viscosity of 0.7 Pa·s at 20°C, an amine value of 158.6 mg KOH/g and a crystallization temperature of -66.5°C.

Aldimine R-1:
100.00 g of aldehyde-2 was introduced into the round bottom flask under nitrogen atmosphere. 27.86 g of 3-aminomethyl-3,5,5-trimethylcyclohexylamine (Vestamin® IPD, from Evonik) are added with stirring, after which the volatile components are removed at 80° C. and under reduced pressure of 10 mbar. It was removed with . A pale yellow odorless liquid was obtained with a viscosity of 25.3 Pa·s at 20°C, an amine value of 152.1 mg KOH/g and a crystallization temperature of -40.6°C.

Aldimine R-2:
100.00 g of aldehyde-2 was introduced into the round bottom flask under nitrogen atmosphere. 27.20 g of a 70% aqueous solution of 1,6-hexanediamine (from Sigma-Aldrich) were added with stirring, after which the volatile constituents were removed at 80° C. and under reduced pressure of 10 mbar. A pale yellow, odorless liquid was obtained with a viscosity of 1.0 Pa·s at 20°C, an amine value of 169.4 mg KOH/g and a crystallization temperature of -63.8°C.

Aldimine R-3:
50.00 g of aldehyde-3 was introduced into the round bottom flask under nitrogen atmosphere. 13.93 g of 3-aminomethyl-3,5,5-trimethylcyclohexylamine (Vestamin® IPD, from Evonik) are added with stirring, after which the volatile components are removed at 80° C. and under reduced pressure of 10 mbar. It was removed with . A pale yellow, odorless liquid was obtained with a viscosity of 0.2 Pa·s at 20° C. and an amine value of 153.0 mg KOH/g.

Aldimines A-1 and A-2 are latent curing agents according to the invention and correspond to formula (IV).

Aldimines R-1 and R-2 and R-3 are used as comparisons.

Preparation of polymers containing isocyanate groups Polymer P1:
400 g of polyoxypropylene diol (Acclaim® 4200, from Covestro; OH number 28.5 mg KOH/g) and 52 g of diphenylmethane 4,4'-diisocyanate (Desmodur® 44 MC L, from Covestro) were reacted by known processes at 80° C. to obtain an NCO-terminated polyurethane polymer which is liquid at room temperature and has a content of free isocyanate groups of 1.85% by weight.

Polymer P2:
590 g of polyoxypropylene diol (Acclaim® 4200, manufactured by Covestro; OH number 28.5 mg KOH/g), 1180 g of polyoxypropylene/polyoxyethylene triol (Caradol® MD34-02, manufactured by Shell; OH number 35.0 mg KOH/g) and 230 g of isophorone diisocyanate (Vestanat® IPDI, manufactured by Evonik) were reacted at 80° C. by a known process to give a solution which is liquid at room temperature and 2.10% by weight free. An NCO-terminated polyurethane polymer with a content of isocyanate groups was obtained.

Polymer P3:
300.0 g of polyoxypropylene/polyoxyethylene diol (Desmophen® L300, manufactured by Covestro; OH number 190.0 mg KOH/g) and 228.8 g of isophorone diisocyanate (Vestanat® IPDI, manufactured by Evonik) was reacted by known processes at 60° C. to obtain an NCO-terminated polyurethane polymer which is liquid at room temperature and has a content of free isocyanate groups of 7.91% by weight.

Polyurethane composition (one component)
Compositions Z1 to Z6
For each composition, the ingredients specified in Table 1 were mixed in the amounts specified (in parts by weight) using a centrifugal mixer (SpeedMixer ^™ DAC 150, FlackTek Inc.) with water removed at 3000 rpm for 1 minute. . Each composition was tested as follows.

As a measure of storage stability, viscosity (1d RT) was measured the day after manufacture and viscosity (7d 60°C) after 7 days of storage in a closed container in a warm circulation oven at 60°C as described above. did.

Stick-free time was measured as a measure of open time. For this purpose, a few grams of the composition are applied to cardboard with a layer thickness of about 2 mm and under standard climatic conditions, and when the surface of the composition is gently dabbed with an LDPE pipette, no residue is removed. The time until it no longer remained on the pipette for the first time was measured.

To measure the mechanical properties, each composition was poured onto a PTFE coated film to obtain a 2 mm thick film and stored for 7 days under standard climatic conditions, with a bar length of 30 mm and a bar width of 4 mm. , several dumbbells with a length of 75 mm were punched out from the film and these were measured for tensile strength (load at break), elongation at break, modulus of elasticity 5% (at elongation between 0.5% and 5%) and elasticity. Tested according to DIN EN 53504 at a tensile rate of 200 mm/min for a ratio of 50% (from 0.5% to 50% elongation).

The appearance of the produced film was visually evaluated. "Good" was used to describe a colorless, transparent film with a bubble-free, non-tacky surface.

Odor was evaluated by sniffing at a distance of 2 cm from the freshly prepared film. "Present" means that the odor was clearly felt. "None" means that no odor was detected.

The results are reported in Table 1.

Compositions marked with (Ref) are comparative examples.

Compositions Z7 to Z10
For each composition, the ingredients specified in Table 2 were mixed in the specified amounts (parts by weight) using a centrifugal mixer (SpeedMixer™ DAC 150, FlackTek Inc.) at 3000 rpm for 1 minute with moisture protection. The mixture was mixed and stored in a moisture-proof manner. Each composition was tested as follows.

The formation of spots on the cardboard was determined as a measure of plasticizer migration. For this purpose, each composition was applied to cardboard strips with a round base area of 15 mm diameter and 4 mm height and stored under standard climatic conditions for 7 days. A dark oval stain was then formed around each composition on the cardboard. Its dimensions (height and width) were measured and reported as migration in Table 2.

The invention disclosed herein includes the following aspects:
[1]
- 70% to 95% by weight of formula (I)

(wherein R is an alkyl group having 6 to 20 carbon atoms)
aldehyde, and
- 5% to 30% by weight of an alkylbenzene compound not corresponding to the above formula (I);
Use of aldehyde mixtures containing aldehydes as blocking agents for amines.
[2] The use according to [1] above, wherein the alkylbenzene compound that does not correspond to the formula (I) has a boiling point higher than the aldehyde of the formula (I).
[3] The use according to [1] or [2] above, wherein the alkyl group R is mainly branched.
[4] The use according to any one of [1] to [3] above, wherein the formyl group is in the para position.
[5] The aldehyde of formula (I) is selected from 4-decylbenzaldehyde, 4-undecylbenzaldehyde, 4-dodecylbenzaldehyde, 4-tridecylbenzaldehyde and 4-tetradecylbenzaldehyde, and the alkyl group of the aldehyde The use according to any one of [1] to [4] above, wherein is mainly branched.
[6] The alkylbenzene compound that does not correspond to the formula (I) has the formula

(wherein R' is an alkylene group having 6 to 20 carbon atoms)
The use according to any one of [1] to [5] above, characterized in that it contains one or more compounds.
[7] The aldehyde mixture has the formula

The use according to any one of [1] to [6] above, characterized in that it is a reaction product of formylation of at least one alkylbenzene.
[8] The use according to [7] above, wherein the formylation is carried out in the presence of hydrofluoric acid and boron trifluoride together with carbon monoxide.
[9] The amine to be blocked contains at least one primary or secondary amino group, and additionally at least one selected from primary amino groups, secondary amino groups, hydroxyl groups, and silane groups. The use according to any one of [1] to [8] above, characterized in that the method has two reactive groups.
[10] The amines to be blocked include primary aliphatic diamines, primary aromatic diamines, primary aliphatic triamines, aliphatic diamines having primary and secondary amino groups, two primary Any one of [1] to [9] above, characterized in that it is selected from the group consisting of aliphatic polyamines having primary and secondary amino groups, amino alcohols, dialkanolamines, aminosilanes, and alkanolaminosilanes. Uses as described in.
[11] The aldehyde mixture reacts with the amine to be blocked, thereby
- said aldehyde mixture, optionally with the addition of a solvent, combines with said amine to give a reaction mixture, the aldehyde groups being in stoichiometric or stoichiometric amounts with respect to said primary and secondary amino groups; present in excess amount, and
- the water of condensation produced in said reaction, and optionally the solvent used during or after said combination, is removed from said reaction mixture using a suitable method, optionally involving heating of said reaction mixture and/or application of reduced pressure. The use according to any one of [1] to [10] above, characterized in that it is removed by.
[12] A blocked amine obtained from the use of the aldehyde mixture according to any one of [1] to [11] above.
[13] Formula (II) and/or (III)

(In the formula,
X is O, S, or NR ⁰ , where R ⁰ is a monovalent organic group having 1 to 18 carbon atoms,
Y is an optionally substituted 1,2-ethylene or 1,3-propylene group)
The blocked amine according to [12] above, which has a functional group of:
[14] A composition containing an isocyanate group containing at least one blocked amine according to any one of [11] to [13] above.
[15]
- at least one polyisocyanate and/or at least one polyurethane polymer containing isocyanate groups, and
- Formula (IV)

(In the formula,
n is 2 or 3,
A is an n-valent organic group with a molecular weight in the range of 28 to 10,000)
at least one polyaldimine of
The isocyanate group-containing composition according to [14] above, which comprises:

Claims (15)

- 70% to 95% by weight of formula (I)

(wherein R is an alkyl group having 10 to 14 carbon atoms)
and - the use of an aldehyde mixture comprising from 5% by weight to 30% by weight of an alkylbenzene compound not having the structure of formula (I) as a blocking agent for amines. 2. Use according to claim 1, characterized in that the alkylbenzene compound without the structure of formula (I) has a higher boiling point than the aldehyde of formula (I). Use according to claim 1 or 2, characterized in that the alkyl group R is branched. Use according to any one of claims 1 to 3, characterized in that the formyl group is in the para position. The aldehyde of formula (I) is selected from 4-decylbenzaldehyde, 4-undecylbenzaldehyde, 4-dodecylbenzaldehyde, 4-tridecylbenzaldehyde and 4-tetradecylbenzaldehyde, and the alkyl group of the aldehyde is branched. Use according to any one of claims 1 to 4, characterized in that: The alkylbenzene compound not having the structure of the formula (I) has the formula

(wherein R' is an alkylene group having 6 to 20 carbon atoms)
Use according to any one of claims 1 to 5, characterized in that it comprises one or more compounds. The aldehyde mixture has the formula

The use according to any one of claims 1 to 6, characterized in that it is a reaction product of the formylation of at least one alkylbenzene. 8. Use according to claim 7, characterized in that the formylation was carried out in the presence of hydrofluoric acid and boron trifluoride with carbon monoxide. The amine to be blocked has at least one primary or secondary amino group and additionally at least one reactive group selected from primary amino groups, secondary amino groups, hydroxyl groups and silane groups. Use according to any one of claims 1 to 8, characterized in that it has. The amines to be blocked include primary aliphatic diamines, primary aromatic diamines, primary aliphatic triamines, aliphatic diamines having primary and secondary amino groups, two primary and The use according to any one of claims 1 to 9, characterized in that it is selected from the group consisting of aliphatic polyamines having secondary amino groups, amino alcohols, dialkanolamines, aminosilanes and alkanol-aminosilanes. The aldehyde mixture reacts with the amine to be blocked, thereby
- the aldehyde mixture, optionally with the addition of a solvent, combines with the amine to give a reaction mixture, the aldehyde groups being present in stoichiometric amounts with respect to the primary and secondary amino groups of the amine to be blocked; or present in stoichiometric excess, and - the water of condensation produced in said reaction, and optionally the solvent used during or after said compounding, is removed from said reaction mixture, optionally by heating said reaction mixture and Use according to any one of claims 1 to 10, characterized in that it is removed using a suitable method involving the application of reduced pressure. A mixture comprising an amine blocked by an aldehyde of formula (I) obtained from the use of an aldehyde mixture according to any one of claims 1 to 11. The amine blocked by the aldehyde of formula (I) is of formula (II) and/or (III)

(In the formula,
X is O, or S, or NR ⁰ , where R ⁰ is a monovalent organic group having 1 to 18 carbon atoms;
Y is an optionally substituted 1,2-ethylene or 1,3-propylene group)
13. A mixture according to claim 12, characterized in that it has a functional group of . A composition containing a compound having isocyanate groups , comprising at least one blocked amine contained in a mixture according to claim 12 or 13. - at least one polyisocyanate and/or at least one polyurethane polymer containing isocyanate groups, and - formula (IV)

(In the formula,
n is 2 or 3,
A is an n-valent organic group with a molecular weight in the range of 28 to 10,000)
15. A composition containing a compound having isocyanate groups according to claim 14, characterized in that it contains at least one polyaldimine.